JP6328114B2 - Method for preparing a catalyst material - Google Patents
Method for preparing a catalyst material Download PDFInfo
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- JP6328114B2 JP6328114B2 JP2015525939A JP2015525939A JP6328114B2 JP 6328114 B2 JP6328114 B2 JP 6328114B2 JP 2015525939 A JP2015525939 A JP 2015525939A JP 2015525939 A JP2015525939 A JP 2015525939A JP 6328114 B2 JP6328114 B2 JP 6328114B2
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- metal
- metals
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- thin film
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- 239000003054 catalyst Substances 0.000 title claims description 124
- 239000000463 material Substances 0.000 title claims description 76
- 238000000034 method Methods 0.000 title claims description 54
- 229910052751 metal Inorganic materials 0.000 claims description 113
- 239000002184 metal Substances 0.000 claims description 113
- 239000010410 layer Substances 0.000 claims description 89
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 62
- 239000010409 thin film Substances 0.000 claims description 52
- 238000000576 coating method Methods 0.000 claims description 45
- 150000002739 metals Chemical class 0.000 claims description 45
- 239000011248 coating agent Substances 0.000 claims description 43
- 229910052697 platinum Inorganic materials 0.000 claims description 28
- 238000009501 film coating Methods 0.000 claims description 12
- 239000012876 carrier material Substances 0.000 claims description 11
- 239000000835 fiber Substances 0.000 claims description 11
- -1 platinum group metals Chemical class 0.000 claims description 11
- 229910045601 alloy Inorganic materials 0.000 claims description 10
- 239000000956 alloy Substances 0.000 claims description 10
- 238000000231 atomic layer deposition Methods 0.000 claims description 10
- 239000012790 adhesive layer Substances 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 5
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 4
- 239000010953 base metal Substances 0.000 claims description 4
- 239000011236 particulate material Substances 0.000 claims description 4
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052737 gold Inorganic materials 0.000 claims description 3
- 239000010931 gold Substances 0.000 claims description 3
- 229910052709 silver Inorganic materials 0.000 claims description 3
- 239000004332 silver Substances 0.000 claims description 3
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 2
- 238000000277 atomic layer chemical vapour deposition Methods 0.000 claims description 2
- 229910052741 iridium Inorganic materials 0.000 claims description 2
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052762 osmium Inorganic materials 0.000 claims description 2
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 claims description 2
- 229910052763 palladium Inorganic materials 0.000 claims description 2
- 229910052703 rhodium Inorganic materials 0.000 claims description 2
- 239000010948 rhodium Substances 0.000 claims description 2
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 2
- 229910052707 ruthenium Inorganic materials 0.000 claims description 2
- 239000012528 membrane Substances 0.000 description 36
- 239000000446 fuel Substances 0.000 description 27
- 239000007789 gas Substances 0.000 description 21
- 239000000758 substrate Substances 0.000 description 21
- 238000009792 diffusion process Methods 0.000 description 20
- 125000004429 atom Chemical group 0.000 description 17
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 15
- 229910052760 oxygen Inorganic materials 0.000 description 15
- 239000001301 oxygen Substances 0.000 description 15
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 14
- 229910052799 carbon Inorganic materials 0.000 description 12
- 230000000694 effects Effects 0.000 description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 150000002500 ions Chemical group 0.000 description 9
- 239000011859 microparticle Substances 0.000 description 9
- 229920000642 polymer Polymers 0.000 description 9
- 239000004810 polytetrafluoroethylene Substances 0.000 description 9
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 9
- 238000006722 reduction reaction Methods 0.000 description 9
- 230000003197 catalytic effect Effects 0.000 description 8
- 239000010411 electrocatalyst Substances 0.000 description 8
- 239000003792 electrolyte Substances 0.000 description 8
- 150000004767 nitrides Chemical class 0.000 description 8
- 229920000049 Carbon (fiber) Polymers 0.000 description 7
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 7
- 239000004917 carbon fiber Substances 0.000 description 7
- 229910044991 metal oxide Inorganic materials 0.000 description 7
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- 239000006229 carbon black Substances 0.000 description 5
- 235000019241 carbon black Nutrition 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 150000004706 metal oxides Chemical class 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 150000001768 cations Chemical class 0.000 description 4
- 238000005260 corrosion Methods 0.000 description 4
- 230000007797 corrosion Effects 0.000 description 4
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- 230000002269 spontaneous effect Effects 0.000 description 4
- 238000012546 transfer Methods 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 239000004642 Polyimide Substances 0.000 description 3
- 229910001260 Pt alloy Inorganic materials 0.000 description 3
- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 239000004020 conductor Substances 0.000 description 3
- 238000003487 electrochemical reaction Methods 0.000 description 3
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical group OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 229920000557 Nafion® Polymers 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 239000004693 Polybenzimidazole Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- UQZIWOQVLUASCR-UHFFFAOYSA-N alumane;titanium Chemical compound [AlH3].[Ti] UQZIWOQVLUASCR-UHFFFAOYSA-N 0.000 description 2
- 229920006378 biaxially oriented polypropylene Polymers 0.000 description 2
- 239000011127 biaxially oriented polypropylene Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000005229 chemical vapour deposition Methods 0.000 description 2
- 229920001940 conductive polymer Polymers 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 238000004070 electrodeposition Methods 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- UQSQSQZYBQSBJZ-UHFFFAOYSA-N fluorosulfonic acid Chemical compound OS(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-N 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 229910003480 inorganic solid Inorganic materials 0.000 description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 150000002736 metal compounds Chemical class 0.000 description 2
- 229910003455 mixed metal oxide Inorganic materials 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000005240 physical vapour deposition Methods 0.000 description 2
- 229920002480 polybenzimidazole Polymers 0.000 description 2
- 229920005597 polymer membrane Polymers 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 238000011946 reduction process Methods 0.000 description 2
- 238000009987 spinning Methods 0.000 description 2
- 238000004544 sputter deposition Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 2
- 229910001887 tin oxide Inorganic materials 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- MTPVUVINMAGMJL-UHFFFAOYSA-N trimethyl(1,1,2,2,2-pentafluoroethyl)silane Chemical compound C[Si](C)(C)C(F)(F)C(F)(F)F MTPVUVINMAGMJL-UHFFFAOYSA-N 0.000 description 2
- UONOETXJSWQNOL-UHFFFAOYSA-N tungsten carbide Chemical compound [W+]#[C-] UONOETXJSWQNOL-UHFFFAOYSA-N 0.000 description 2
- 229920003934 Aciplex® Polymers 0.000 description 1
- 229920003937 Aquivion® Polymers 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229920003935 Flemion® Polymers 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 108700038980 S-((2-chloroethyl)carbamoyl)glutathione Proteins 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 1
- 239000002800 charge carrier Substances 0.000 description 1
- 238000005234 chemical deposition Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000002322 conducting polymer Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- 238000006056 electrooxidation reaction Methods 0.000 description 1
- 238000001523 electrospinning Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 229920001477 hydrophilic polymer Polymers 0.000 description 1
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- 229920001600 hydrophobic polymer Polymers 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
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- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 239000010955 niobium Substances 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
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- 229920000412 polyarylene Polymers 0.000 description 1
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- 229920001296 polysiloxane Polymers 0.000 description 1
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- 150000003460 sulfonic acids Chemical class 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
- H01M4/8825—Methods for deposition of the catalytic active composition
- H01M4/8842—Coating using a catalyst salt precursor in solution followed by evaporation and reduction of the precursor
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/8647—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites
- H01M4/8657—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites layered
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
- H01M4/8825—Methods for deposition of the catalytic active composition
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
- H01M4/8878—Treatment steps after deposition of the catalytic active composition or after shaping of the electrode being free-standing body
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/9041—Metals or alloys
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/9075—Catalytic material supported on carriers, e.g. powder carriers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/92—Metals of platinum group
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/92—Metals of platinum group
- H01M4/921—Alloys or mixtures with metallic elements
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/92—Metals of platinum group
- H01M4/925—Metals of platinum group supported on carriers, e.g. powder carriers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M2008/1095—Fuel cells with polymeric electrolytes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Description
本発明は、触媒材料を調製するための新規な方法に関するものであり、電気化学的装置中、特に、プロトン交換膜燃料電池のような燃料電池中の電極用の触媒材料を調製するための方法に関する。 The present invention relates to a novel method for preparing a catalyst material, and a method for preparing a catalyst material for an electrode in an electrochemical device, in particular a fuel cell such as a proton exchange membrane fuel cell. About.
燃料電池は、電解質により分離される２つの電極を含む電気化学的電池である。水素又はメタノール若しくはエタノール等のアルコールのような燃料は、アノードに供給され、酸素又は空気のようなオキシダントは、カソードに供給される。電気化学反応は電極で起こり、燃料及びオキシダントの化学エネルギーは、電気エネルギー及び熱に変換される。電極触媒は、アノードにおける燃料の電気化学的酸化反応及びカソードにおける酸素の電気化学的還元反応を促進するために使用される。 A fuel cell is an electrochemical cell that includes two electrodes separated by an electrolyte. A fuel such as hydrogen or alcohol such as methanol or ethanol is supplied to the anode and an oxidant such as oxygen or air is supplied to the cathode. The electrochemical reaction takes place at the electrode, and the chemical energy of the fuel and oxidant is converted into electrical energy and heat. Electrocatalysts are used to promote the electrochemical oxidation of fuel at the anode and the electrochemical reduction of oxygen at the cathode.
プロトン交換膜（ＰＥＭ）燃料電池中で、電解質は、固体高分子膜である。該膜は、電子遮蔽性であるがプロトン伝導性であり、アノードで生成されるプロトンは、該膜を通過してカソードに運ばれ、そこで酸素と結合して水を生成する。 In proton exchange membrane (PEM) fuel cells, the electrolyte is a solid polymer membrane. The membrane is electron blocking but proton conducting, and the protons generated at the anode are transported through the membrane to the cathode where they combine with oxygen to produce water.
ＰＥＭ燃料電池の主要部品は、膜−電極接合体（ＭＥＡ)として知られ、基本的に５層からなる。中心層は、イオン伝導性重合体膜である。イオン伝導性重合体膜のどちらかの面に、電極触媒層があり、特定の電気化学反応のために企図される電極触媒を含む。最後に、各電極触媒層に隣接してガス拡散層がある。ガス拡散層は、反応物質が電極触媒層に達することを可能にし、電気化学反応により生成する電流を流さなければならない。従って、ガス拡散層は、多孔性であり、電気伝導性でなければならない。 The main part of a PEM fuel cell, known as a membrane-electrode assembly (MEA), basically consists of five layers. The central layer is an ion conductive polymer film. On either side of the ion conducting polymer membrane is an electrocatalyst layer that contains an electrocatalyst that is intended for a particular electrochemical reaction. Finally, there is a gas diffusion layer adjacent to each electrode catalyst layer. The gas diffusion layer must allow the reactants to reach the electrocatalyst layer and carry the current generated by the electrochemical reaction. Therefore, the gas diffusion layer must be porous and electrically conductive.
燃料の酸化反応及び酸素の還元反応のための電極触媒は、一般に、白金又は一種又は複数種の他の金属を混ぜて合金とされる白金を基礎とする。白金触媒又は白金合金触媒は、不担持のナノメートルサイズの微粒子（メタルブラック又は他の不担持の金属微粒子粉末等）の形態であり得て、又は伝導性炭素基材上に更により大なる表面積の粒子若しくは他の伝導性材料（担持触媒）として付着され得る。 Electrocatalysts for fuel oxidation reactions and oxygen reduction reactions are generally based on platinum, which is alloyed with platinum or one or more other metals. The platinum catalyst or platinum alloy catalyst may be in the form of unsupported nanometer-sized particulates (such as metal black or other unsupported metal particulate powder) or even greater surface area on the conductive carbon substrate. Or as other conductive material (supported catalyst).
ＭＥＡは、いくつかの方法で製造され得る。電極触媒層は、ガス拡散層に塗布され、ガス拡散電極を生成し得る。２つのガス拡散電極は、イオン伝導性膜のどちらかの面に配置され、共に積層され５層ＭＥＡを生成し得る。あるいは、電極触媒層は、イオン伝導性膜の両面に塗布され、触媒で覆われたイオン伝導性膜を生成し得る。その後、ガス拡散層は、触媒で覆われたイオン伝導性膜の両面に塗布される。最後に、ＭＥＡは、一方の面が電極触媒層に覆われたイオン伝導性膜、その電極触媒層に隣接するガス拡散層、及びイオン伝導性膜の他方の面上のガス拡散電極から形成され得る。 The MEA can be manufactured in several ways. The electrode catalyst layer can be applied to the gas diffusion layer to produce a gas diffusion electrode. Two gas diffusion electrodes can be placed on either side of the ion conductive membrane and stacked together to produce a five layer MEA. Alternatively, the electrode catalyst layer can be applied to both sides of the ion conductive membrane to produce an ion conductive membrane covered with a catalyst. Thereafter, the gas diffusion layer is applied to both surfaces of the ion conductive membrane covered with the catalyst. Finally, the MEA is formed from an ion conductive membrane covered on one side with an electrode catalyst layer, a gas diffusion layer adjacent to the electrode catalyst layer, and a gas diffusion electrode on the other side of the ion conductive membrane. obtain.
一般に、何十又は何百のＭＥＡが、大部分の用途のために十分な電力を供給するのに必要とされるので、多数のＭＥＡは、燃料電池スタックを組み立てるために集められる。フローフィールドプレートは、ＭＥＡを隔てるために使用される。該プレートは、いくつかの機能、すなわち、ＭＥＡに反応物質を供給すること、生成物を除去すること、電気の接続を提供すること、及び物理的な担体を提供すること、を実施する。 In general, dozens or hundreds of MEAs are required to provide sufficient power for most applications, so a large number of MEAs are collected to assemble the fuel cell stack. A flow field plate is used to separate the MEAs. The plate performs several functions: supplying reactants to the MEA, removing products, providing electrical connections, and providing physical support.
燃料電池中で使用される現在の最先端の電極触媒は、一般に、伝導性で高表面積の炭素担体上に担持される白金又は白金合金からできている。炭素は、高表面積の白金をほぼ球形構造の別々のナノ微粒子の形で、一般に、生成させる。炭素担体は、ガス状の反応物質と液体の生成物、又は液体の反応物質とガス状の生成物が、電極触媒のナノ微粒子へ移動し、該ナノ微粒子から移動し得る多孔質層を形成する。実際の操作条件では、特に、酸素の還元反応が起こる燃料電池のカソードにおいて、多くの問題が起こり、炭素に担持される触媒は、炭素担体の腐食、白金又は白金合金触媒微粒子の溶解及び焼結を含むため性能の損失をもたらす。そのような触媒に対する更に、そしてより重要な問題は、自動車のドライブトレインにおけるような価格の重要な応用における経済的応用に対して、積層電池からの十分な発電出力のために必要とされる白金の量が多すぎると考えられていることである。従って、特に必要なのは、酸素還元反応のための触媒を改善することである。炭素上に担持される既存のナノ微粒子の白金微粒子が高い白金の表面積（Ｐｔの単位質量当たりの表面積−ｍ２／ｇＰｔ）を有し、一般に、５０ｍ２／ｇＰｔより大きいにもかかわらず、該表面積は、低い固有表面の比活性（触媒表面の単位面積当たり生成する電流−μＡｃｍ２ Ｐｔを単位としての活性）を有し、その時、微粒子は約３ｎｍ以下の直径である（M. Shao, A. Peles, K. Shoemaker, Nano Letters, 11, 3714-3719 (2011)）。このことは、白金の単位質量当たり生成する電流（Ａ／ｍｇＰｔ）を単位としての全体的な質量活性が必要とされるより低い結果になる。その上、この大きさの微粒子は、電位サイクルに対し不十分な抵抗性を有し、迅速に溶解し焼結し得る。最新技術の触媒にとって、高い割合で炭素担体表面積が非被覆のままであることは、一般的でもあり、該触媒は、日常的な操作の間にカソードで起こる高電位で酸化され、及び始動及び停止時に起こり得る更により高電位で酸化され得る。 Current state-of-the-art electrocatalysts used in fuel cells are generally made of platinum or a platinum alloy supported on a conductive, high surface area carbon support. Carbon generally produces high surface area platinum in the form of discrete nanoparticles of approximately spherical structure. The carbon support forms a porous layer in which gaseous reactants and liquid products, or liquid reactants and gaseous products migrate to the electrocatalyst nanoparticles and can migrate from the nanoparticles. . Under actual operating conditions, many problems occur, especially in the cathode of a fuel cell where oxygen reduction reaction occurs, and the catalyst supported on carbon is corrosion of carbon support, dissolution and sintering of platinum or platinum alloy catalyst fine particles. Results in loss of performance. A further and more important issue for such catalysts is the platinum required for sufficient power output from laminated batteries for economic applications in cost-sensitive applications such as in automotive drivetrains. Is considered to be too much. Therefore, what is particularly needed is to improve the catalyst for the oxygen reduction reaction. Despite existing nanoparticulate platinum microparticles supported on carbon having a high platinum surface area (surface area per unit mass of Pt—m 2 / g Pt ), generally greater than 50 m 2 / g Pt , The surface area has a low specific surface specific activity (current generated per unit area of the catalyst surface-activity in μAcm 2 Pt ), at which time the microparticles have a diameter of about 3 nm or less (M. Shao , A. Peles, K. Shoemaker, Nano Letters, 11, 3714-3719 (2011)). This results in a lower overall mass activity required in units of current generated per unit mass of platinum (A / mg Pt ). Moreover, microparticles of this size have insufficient resistance to potential cycling and can dissolve and sinter quickly. For state-of-the-art catalysts, it is also common for the carbon support surface area to remain uncoated at a high rate, which is oxidized at the high potential that occurs at the cathode during routine operation, and start-up and It can be oxidized at even higher potentials that can occur during shutdown.
低表面比活性、及び小さい白金微粒子の不十分な安定性に対する寄与の一つは、低配位部位中の高い数の原子である。低配位部位において原子は、他の白金（金属）原子に対しより少ない結合を有する。例えば、八面体の場合、角の原子は、４個の近接原子のみ有し（配位数＝４）、辺の原子は７個、及び（１１１）面内の原子は９個の近接原子を有する。小さな八面体の場合、大きな八面体と比べ角と辺の部分の割合が高い。低配位部位の原子は、固体微粒子にそれほど強く結合されず、酸素をより強く結合することもできるので、より溶解しやすく、このことは、酸素還元反応を実施することがより難しいことを意味し、金属は水よりもむしろ酸化物を形成する傾向にある。 One contribution to the low surface specific activity and the poor stability of small platinum particles is the high number of atoms in the low coordination sites. At low coordination sites, the atoms have fewer bonds to other platinum (metal) atoms. For example, in the case of an octahedron, the corner atom has only 4 neighboring atoms (coordination number = 4), the side atoms have 7 atoms, and the atoms in the (111) plane have 9 neighboring atoms. Have. In the case of a small octahedron, the ratio of corners and sides is higher than that of a large octahedron. The atoms in the low coordination site are not so strongly bound to the solid particulates and can also bind oxygen more strongly, making it easier to dissolve, which means that it is more difficult to carry out the oxygen reduction reaction However, metals tend to form oxides rather than water.
微粒子が直径３ｎｍよりも長い場合、それらは低配位原子の割合が低く、従ってより安定であり、高比表面活性も有する。しかし、全体的な触媒の表面積がより低いので、これらは一般により低白金質量活性を有する。微粒子の表面のみが電極触媒的に作用するので、より大きな微粒子中の有用な白金金属の大部分は使用されない。 If the microparticles are longer than 3 nm in diameter, they have a low proportion of low coordination atoms and are therefore more stable and also have a high specific surface activity. However, they generally have a lower platinum mass activity due to the lower overall catalyst surface area. Since only the surface of the microparticles acts electrocatalytically, most of the useful platinum metal in the larger microparticles is not used.
欧州特許第１０２１２４６号で開示されるようなポリマーフィブリル上に担持される白金の針状構造のような代替的な構造は、酸素還元反応のための適切な代替的な触媒として提案されてきている。白金構造体の体積比に対する表面積が更に低いので、これらの触媒は、最新技術のナノ微粒子触媒よりも高比活性を有し得るが、従って、白金の表面積も低い（一般に、約１０ｍ２／ｇＰｔ）（燃料電池ハンドブック−基礎、技術、及び応用(Handbook of Fuel Cells − Fundamentals, Technology and Applications)、第３巻）。燃料電池技術と応用(Fuel Cell Technology and Applications)、５７６−５８９ページでは、質量活性は十分に向上されていない。 Alternative structures such as platinum needles supported on polymer fibrils as disclosed in EP 1021246 have been proposed as suitable alternative catalysts for oxygen reduction reactions. . These catalysts may have higher specific activity than state-of-the-art nanoparticulate catalysts because of the lower surface area relative to the volume ratio of the platinum structure, and therefore the surface area of platinum is also lower (generally about 10 m 2 / gPt (Fuel Cell Handbook-Fundamentals, Technology and Applications, Volume 3). In Fuel Cell Technology and Applications, pages 576-589, mass activity is not sufficiently improved.
従って、現在の構造より高質量活性を示し、白金の溶解及び焼結並びに担体腐食にも安定である改良触媒の必要性が残る。国際特許出願ＰＣＴ／ＧＢ２０１３／０５０８１５号、この内容は、出典明示によりここに引用され、（ｉ）担体材料と（ｉｉ）薄膜触媒被覆を含む新規な触媒材料を開示し、該薄膜触媒被覆は≦８ｎｍの平均厚さを有し、該担体材料の表面積の少なくとも４０％は、該薄膜触媒被覆により覆われる。（ｉ）担体材料と（ｉｉ）薄膜触媒被覆を含む触媒材料は、また、該薄膜触媒被覆が少なくとも２５ｍ２／ｇ、適切には少なくとも４０ｍ２／ｇ、好ましくは少なくとも５０ｍ２／ｇの表面積を有することも開示し、担体材料の表面積の少なくとも４０％が該薄膜触媒被覆により覆われる。本願で開示される改善された触媒材料は、最新技術を超えて改善された質量活性を示す。その上、該触媒材料は、溶解、焼結、担体の腐食に対し改善された安定性を示す。薄膜触媒被覆は、プラズマアシストを含む真空法、プラズマアシストを含む気相法、電気化学法、又は化学的堆積法を含むが、それらに限定されない多くの方法により担体材料に塗布され得る。特に、以下の技術：原子層堆積法、電着法、電気泳動法、化学蒸着法、物理蒸着法、プラズマアシスト堆積法、スパッタリング法、蒸発法、が使われ得る。特に好ましい技術は、原子層堆積法である。 Thus, there remains a need for improved catalysts that exhibit higher mass activity than current structures and are stable to platinum dissolution and sintering and support corrosion. International patent application PCT / GB2013 / 050815, the contents of which are hereby incorporated by reference and disclose a novel catalyst material comprising (i) a support material and (ii) a thin film catalyst coating, wherein the thin film catalyst coating is ≦ Having an average thickness of 8 nm, at least 40% of the surface area of the support material is covered by the thin film catalyst coating. A catalyst material comprising (i) a support material and (ii) a thin film catalyst coating also has a surface area of at least 25 m 2 / g, suitably at least 40 m 2 / g, preferably at least 50 m 2 / g. At least 40% of the surface area of the support material is covered by the thin film catalyst coating. The improved catalytic materials disclosed herein exhibit improved mass activity over the state of the art. In addition, the catalyst material exhibits improved stability against melting, sintering and support corrosion. The thin film catalyst coating can be applied to the support material by a number of methods including, but not limited to, vacuum methods including plasma assist, gas phase methods including plasma assist, electrochemical methods, or chemical deposition methods. In particular, the following techniques can be used: atomic layer deposition, electrodeposition, electrophoresis, chemical vapor deposition, physical vapor deposition, plasma assisted deposition, sputtering, evaporation. A particularly preferred technique is atomic layer deposition.
原子層堆積法は、上述の触媒材料に存在するように、連続的な薄膜層の生成に特に適する技術である。しかし、層の連続性が生じる厚さは、表面エネルギー、付着される触媒材料と触媒材料が付着される基材の両方、基材の表面化学、前駆体の熱安定性、及び前駆配位子の反応性を含むが、それらに限定されない多くの要因に大いに依存する。結果として、非常に薄い厚さの連続的な薄膜層を製造することは、しばしば難しい。 Atomic layer deposition is a technique that is particularly suitable for the production of continuous thin film layers, as is present in the catalyst materials described above. However, the thickness at which the layer continuity occurs depends on the surface energy, both the catalyst material deposited and the substrate to which the catalyst material is deposited, the surface chemistry of the substrate, the thermal stability of the precursor, and the precursor ligand. Relies heavily on many factors, including but not limited to: As a result, it is often difficult to produce a continuous thin film layer of very thin thickness.
白金の連続的な薄膜層は、酸素還元電極触媒について興味のある構造である。白金ナノ微粒子よりも単位面積当たりより大きな反応性を示すこと、並びに溶解及び焼結の結果として作用面積の損失に対してより良い安定性を示すことが期待される。白金の価格が原因で、これらの利点が経済原価で理解されるため、白金の層は、非常に薄くなければならず、白金原子層堆積により一般に入手可能であるよりも薄い。更に、基材に対する白金の粘着力は、白金が白金原子層堆積により塗布された場合、十分でないかもしれない。 A continuous thin film layer of platinum is an interesting structure for oxygen reduction electrocatalysts. It is expected to show greater reactivity per unit area than platinum nanoparticles, and better stability against loss of working area as a result of melting and sintering. Due to the price of platinum, these benefits are understood at economic cost, so the platinum layer must be very thin and thinner than is generally available by platinum atomic layer deposition. Furthermore, the adhesion of platinum to the substrate may not be sufficient when platinum is applied by platinum atomic layer deposition.
本発明者らは、上記の特許明細書に記載されているような触媒材料を調製するための方法を提供してきている。従って、本発明は、（ｉ）担体材料と（ｉｉ）薄膜触媒被覆とを含む触媒材料を調製するための方法であって、前記被覆は、一種又は複数種の第一金属及び任意に第二金属を含み、前記方法は、
（ｉ）該担体材料上に第二金属の多層薄膜被覆を設ける工程、及び
（ｉｉ）前記一種又は複数種の第一金属による第二金属の少なくとも一部の自発的なガルバニック置換工程、
を含み、
該第二金属は、該一種又は複数種の第一金属よりも貴でない。
The inventors have provided methods for preparing catalytic materials as described in the above patent specifications. Accordingly, the present invention is a method for preparing a catalyst material comprising (i) a support material and (ii) a thin film catalyst coating, wherein the coating comprises one or more first metals and optionally a second metal. Comprising a metal, the method comprising:
(I) providing a multilayer thin film coating of a second metal on the support material; and (ii) a spontaneous galvanic replacement step of at least a portion of the second metal with the one or more first metals.
Including
The second metal is less noble than the one or more first metals.
「貴でない」との語句は、第一金属と比較した電気化学系列における第二金属の位置を示し、第二金属は、第一金属よりも標準電極電位（Ｅ０)がより負の値である。 The phrase “not noble” indicates the position of the second metal in the electrochemical series compared to the first metal, which has a more negative standard electrode potential (E 0 ) than the first metal. is there.
一種又は複数種の第一金属は、白金族金属（白金、パラジウム、ロジウム、ルテニウム、イリジウム、及びオスミウム）、金若しくは銀、又は卑金属からなる群から適切に選択される。より適切には、一種又は複数種の第一金属は、白金族金属、金、及び銀からなる群から選択され、特に、白金から選択される。適切には一種、二種、又は三種の第一金属があり、より適切には一種の第一金属又は二種の第一金属がある。 One or more kinds of first metals are appropriately selected from the group consisting of platinum group metals (platinum, palladium, rhodium, ruthenium, iridium, and osmium), gold or silver, or base metals. More suitably, the one or more first metals are selected from the group consisting of platinum group metals, gold and silver, in particular platinum. Suitably there are one, two or three primary metals, more suitably there is one primary metal or two primary metals.
第二金属は、適切には卑金属、例えば、遷移金属、例えば、第一遷移金属であり、特に、鉄、コバルト、ニッケル、及び銅である。 The second metal is suitably a base metal, for example a transition metal, for example a first transition metal, in particular iron, cobalt, nickel and copper.
工程（ｉ）は、担体材料上に第二金属の多層薄膜被覆を設けるいかなる方法により実施されてもよく、例えば、原子層堆積法、化学蒸着法、又はメッキ法による。多層被覆は、少なくとも２個の原子の膜厚の被覆であり、２から１００個の原子の膜厚、例えば、２から５０個の原子の膜厚である。好ましくは、第二金属は、原子層堆積法により担体材料上に付着される。あるいは、二段階プロセスが使用され得て、そこで第二金属の化合物、例えば、窒化物は、適切には上記の技術の一つにより、好ましくは原子層堆積法により、担体材料に塗布され、次いで還元プロセスにより第二金属の化合物を第二金属に還元する。還元プロセスは、適切ないかなる還元剤、例えば、水素を用いて実施され得る。第二金属の多層薄膜被覆は、少なくとも４０％の担体材料の表面積、適切には少なくとも５０％、より適切には少なくとも６０％、更に適切には少なくとも７５％、好ましくは少なくとも９０％、及び最も好ましくは少なくとも９５％の担体材料の表面積を覆う。一つの実施態様において、第二金属の多層薄膜被覆は、１００％の担体材料の表面積を覆う。任意に第二金属の多層薄膜被覆の表面は、その表面積を増やすために、化学的又は電気化学的処理プロセスにより粗面化又は構造化され得る。 Step (i) may be performed by any method of providing a multilayer thin film coating of a second metal on a support material, for example, by atomic layer deposition, chemical vapor deposition, or plating. A multi-layer coating is a coating with a thickness of at least 2 atoms and a thickness of 2 to 100 atoms, for example a thickness of 2 to 50 atoms. Preferably, the second metal is deposited on the support material by atomic layer deposition. Alternatively, a two-stage process can be used, where a second metal compound, such as a nitride, is applied to the support material, suitably by one of the techniques described above, preferably by atomic layer deposition, and then The second metal compound is reduced to the second metal by a reduction process. The reduction process can be carried out using any suitable reducing agent, for example hydrogen. The multilayer thin film coating of the second metal has a surface area of at least 40% support material, suitably at least 50%, more suitably at least 60%, more suitably at least 75%, preferably at least 90%, and most preferably Covers at least 95% of the surface area of the support material. In one embodiment, the second metal multilayer thin film coating covers 100% of the surface area of the support material. Optionally, the surface of the second metal multilayer thin film coating can be roughened or structured by chemical or electrochemical treatment processes to increase its surface area.
工程（ｉｉ）は、自発的ガルバニック置換により実施される。第二金属の多層薄膜被覆を伴う担体材料は、一種又は複数種の第一金属のカチオンを含有する溶液にさらされる。第二金属は酸化され、生じたカチオンは溶液中に入る一方、同時に一種又は複数種の第一金属のカチオンは還元され、該一種又は複数種の第一金属は、第二金属の表面上又は担体材料上に付着される。このように、第二金属被覆は、次第に溶解され、一種又は複数種の第一金属、及び任意のいかなる残りの第二金属を含む薄膜触媒被覆がその場所で生成する。一般的に、自発的ガルバニック置換は、開回路状態で実施されるであろう。しかし、被覆された基材と適切な対極の両方、及び一種又は複数種の第一金属の溶液中に浸される参照電極について、定電位電解装置を接続することによる電位制御の用途で使用され得る。ガルバニック置換の間の電位の適切な制御は、薄膜触媒被覆の形態を制御するために使用される。薄膜触媒被覆は、少なくとも４０％の担体材料の表面積、適切には少なくとも５０％、より適切には少なくとも６０％、更により適切には少なくとも７５％、好ましくは少なくとも９０％、及び最も好ましくは少なくとも９５％の担体材料の表面積を覆う。一つの実施態様において、薄膜触媒被覆は、１００％の担体材料の表面積を覆う。 Step (ii) is performed by spontaneous galvanic replacement. The support material with the second metal multilayer thin film coating is exposed to a solution containing one or more first metal cations. The second metal is oxidized and the resulting cation enters the solution while at the same time the cation of the one or more first metals is reduced and the one or more first metals are on the surface of the second metal or Deposited on the carrier material. In this way, the second metal coating is gradually dissolved, and a thin film catalyst coating comprising one or more first metals, and any remaining second metal, is produced there. In general, spontaneous galvanic replacement will be performed in an open circuit state. However, for both coated substrates and appropriate counter electrodes, and for reference electrodes that are immersed in a solution of one or more first metals, they are used in potential control applications by connecting a potentiostat. obtain. Appropriate control of the potential during galvanic substitution is used to control the morphology of the thin film catalyst coating. The thin film catalyst coating has a surface area of at least 40% support material, suitably at least 50%, more suitably at least 60%, even more suitably at least 75%, preferably at least 90%, and most preferably at least 95. % Of the surface area of the carrier material. In one embodiment, the thin film catalyst coating covers 100% of the surface area of the support material.
本発明の第１の態様において、第二金属の全体の多層薄膜被覆は、一種又は複数種の第一金属で置換され、結果として一種又は複数種の第一金属からなる薄膜触媒被覆を有する担体材料になる（図１ａ参照）。 In the first aspect of the present invention, the entire multilayer thin film coating of the second metal is replaced with one or more first metals, and as a result, a carrier having a thin film catalyst coating comprising one or more first metals. It becomes a material (see FIG. 1a).
本発明の第二の態様において、第二金属の多層薄膜被覆は、一種又は複数種の第一金属で完全には置換されず、結果として一種又は複数種の第一金属及びいくらかの第二金属を含む薄膜触媒被覆を有する担体材料になる。このような部分的な置換は、第一金属のカチオンを含有する溶液に接触する時間、溶液の濃度、温度などの条件を制御することによりもたらされ得る。適切には、１０から９９．５原子％の第二金属が一種又は複数種の第一金属により置換される。 In the second aspect of the invention, the multilayer thin film coating of the second metal is not completely replaced with the one or more first metals, resulting in one or more first metals and some second metals. To a support material having a thin film catalyst coating. Such partial substitution can be effected by controlling conditions such as time of contact with the solution containing the first metal cation, solution concentration, temperature, and the like. Suitably 10 to 99.5 atom% of the second metal is replaced by one or more first metals.
本発明の第二の態様の第一の実施態様において、第一金属と第二金属がほとんど又は決して混合しないように、一種又は複数種の第一金属と残りの第二金属は、薄膜触媒被覆中の異なる層中にある（図１ｂ参照）。適切には、８０から９９．５原子％の第二金属が一種又は複数種の第一金属により置換される。 In the first embodiment of the second aspect of the present invention, the one or more first metals and the remaining second metal are thin film catalyst coated so that the first metal and the second metal are scarcely or never mixed. In different layers (see FIG. 1b). Suitably 80 to 99.5 atomic percent of the second metal is replaced by one or more first metals.
第二の実施態様において、一種又は複数種の第一金属の少なくとも一部と残りの第二金属の少なくとも一部が合金を形成する。適切には、１０から８０原子％の第二金属が一種又は複数種の第一金属により置換される。このような合金の形成は、更なる加工工程、例えば、１５０℃から１５００℃、適切には３００℃から１０００℃の温度での熱処理を必要とし得る。合金にする範囲は、一種又は複数種の第一金属：第二金属の比、熱処理の温度、熱処理の時間、及び熱処理プロセスの雰囲気により制御され得る。条件に従って、薄膜触媒被覆は、一種又は複数種の第一金属と残りの第二金属（すなわち、自発的なガルバニック置換反応の後に残された第二金属）の合金を含み得る（図１ｃ参照）。あるいは、薄膜触媒被覆は、（ｉ）一種又は複数種の第一金属と残りの第二金属の一部との合金を含む外側の層、及び合金層と基材との間の残りの第二金属の他の一部の異なる層（図１ｄ参照）、又は（ｉｉ）一種又は複数種の第一金属の外側の層、及び一種又は複数種の第一金属と一種又は複数種の第一金属と基材との間の残りの第二金属との合金を含む異なる層（図１ｅ参照）、又は（ｉｉｉ）一種又は複数種の第一金属の外側の層、基材に隣接する残りの第二金属の一部の層、及び一種又は複数種の第一金属の外側の層と第二金属の層の間に挟まれ、一種又は複数種の第一金属と残りの第二金属の他の一部との合金を含む層（図１ｆ参照）、を含み得る。 In the second embodiment, at least part of one or more first metals and at least part of the remaining second metal form an alloy. Suitably 10 to 80 atomic percent of the second metal is replaced by one or more first metals. The formation of such an alloy may require further processing steps, such as heat treatment at a temperature of 150 ° C. to 1500 ° C., suitably 300 ° C. to 1000 ° C. The range of alloying can be controlled by the ratio of one or more first metals: second metals, the temperature of the heat treatment, the time of the heat treatment, and the atmosphere of the heat treatment process. Depending on the conditions, the thin film catalyst coating may comprise an alloy of one or more first metals and the remaining second metal (ie, the second metal left after the spontaneous galvanic substitution reaction) (see FIG. 1c). . Alternatively, the thin film catalyst coating comprises (i) an outer layer comprising an alloy of one or more first metals and a portion of the remaining second metal, and the remaining second between the alloy layer and the substrate. Some other different layers of metal (see FIG. 1d), or (ii) the outer layer of one or more first metals, and one or more first metals and one or more first metals A different layer comprising an alloy of the remaining second metal between the substrate and the substrate (see FIG. 1e), or (iii) the outer layer of one or more first metals, the remaining second adjacent to the substrate Some layers of two metals, and one or more first metal outer layers and second metal layers sandwiched between one or more first metals and the other second metal other A layer comprising an alloy with a portion (see FIG. 1f) may be included.
一種又は複数種の第一金属と残りの第二金属のこのような合金の形成は、第二金属の選択に従い活性が増加することになり得る。更なる実施態様において、次の工程段階は、例えば、該次の工程段階の前の薄膜触媒被覆と比較して、一種又は複数種の第一金属及び／又は第二金属中で使い果たされてきている薄膜触媒被覆を供給する選択的浸出法により、一種又は複数種の第一金属及び／又は第二金属が合金から取り除かれ、あるいは部分的に取り除かれること、すなわち「非合金の」薄膜触媒被覆を形成すること、で実施される。 Formation of such an alloy of one or more first metals and the remaining second metal can increase activity according to the choice of the second metal. In a further embodiment, the next process step is used up in one or more of the first and / or second metal compared to, for example, a thin film catalyst coating prior to the next process step. One or more of the first and / or second metals are removed or partially removed from the alloy by a selective leaching method to provide the thin film catalyst coatings that are coming up, ie “non-alloyed” thin films Forming a catalyst coating.
本方法の工程（ｉ）で形成される多層被覆の厚さは、薄膜触媒被覆の最終的な構造に依存するであろう。例えば、図１ａによる薄膜触媒被覆を提供するために工程（ｉ）で形成される多層被覆の厚さは、図１ｂからｆによる薄膜触媒被覆を提供するために工程（ｉ）で形成される多層被覆の厚さよりも、より少ない多層の原子を必要とする。 The thickness of the multilayer coating formed in step (i) of the method will depend on the final structure of the thin film catalyst coating. For example, the thickness of the multilayer coating formed in step (i) to provide the thin film catalyst coating according to FIG. 1a is the same as the multilayer formed in step (i) to provide the thin film catalyst coating according to FIGS. Requires fewer layers of atoms than the thickness of the coating.
工程（ｉ）及び／又は（ｉｉ）は、薄膜触媒被覆中の更なる層を提供するために必要に応じて繰り返され得る。例えば、一つの実施態様において、工程（ｉ）を含み、その後一回目と二回目の工程（ｉｉ）に続く方法が実施されてもよく、あるいは、工程（ｉ）と工程（ｉｉ）を含み、その後二回目の工程（ｉ）、次に二回目の工程（ｉｉ）に続く方法が実施されてもよい。当業者は、使用され得る工程（ｉ）と（ｉｉ）を含む多くの変形があり、このような変形の全てが本発明の範囲内にあることを認識するであろう。 Steps (i) and / or (ii) can be repeated as necessary to provide additional layers in the thin film catalyst coating. For example, in one embodiment, a method comprising step (i) followed by the first and second step (ii) may be performed, or alternatively comprising step (i) and step (ii), Thereafter, a method following the second step (i) and then the second step (ii) may be performed. One skilled in the art will recognize that there are many variations including steps (i) and (ii) that can be used, and all such variations are within the scope of the invention.
本発明の更なる態様において、粘着層は、第二金属の多層薄膜被覆を提供する前に、担体材料に塗布される。このような粘着層は、担体材料上に第二金属の核生成を促進するであろう。粘着層は、適切には導電性であり、酸化物、窒化物、又は炭化物、例えば、金属窒化物又は混合金属窒化物（例えば、窒化チタン又は窒化チタンアルミニウム）、ドープ及び混合酸化物（例えば、ニオブドープチタニア及び混合白金族金属酸化物（例えば、IｒＲｕＯＸ又は上記のＰＣＴ／ＧＢ２０１１／０５２４７２号で開示されているもの））を含む金属酸化物、炭素−又はホウ素−ドープダイアモンドであり得る。適切には、粘着層は、原子層堆積法、電着法、電気泳動法、化学蒸着法、物理蒸着法、プラズマアシスト堆積法、スパッタリング法、蒸発法により付着される。 In a further embodiment of the invention, the adhesive layer is applied to the carrier material prior to providing a multilayer thin film coating of the second metal. Such an adhesive layer will promote nucleation of the second metal on the support material. The adhesion layer is suitably conductive and is an oxide, nitride or carbide, such as a metal nitride or mixed metal nitride (e.g. titanium nitride or titanium aluminum nitride), doped and mixed oxide (e.g. It can be a metal oxide, carbon- or boron-doped diamond, including niobium-doped titania and mixed platinum group metal oxides (eg IrRuO X or those disclosed in PCT / GB2011 / 052472 mentioned above). Suitably, the adhesion layer is applied by atomic layer deposition, electrodeposition, electrophoresis, chemical vapor deposition, physical vapor deposition, plasma assisted deposition, sputtering, evaporation.
薄膜触媒被覆の形態は、様々な異なる形状であり得る成分として存在するが、厚さ方向よりも大きい横方向寸法を有する薄膜の成分により全て特徴づけられる。該成分の境界線は、円形、長方形、六角形、又は他の既知の幾何形状であってもよく、境界線の形状が不規則であってもよい。該成分は、隣接成分間の接触なく、不連続であってもよく、隣接成分に接触してもよく、又は一の成分が他に溶け込むように隣接成分と明確に結合してもよい。成分の完全な結合が起こると、本発明の薄膜は、連続的になる。本発明の方法により製造されるいかなる触媒材料において、薄く連続的な膜で覆われる基材上の部位、不連続の成分の部位、及び結合又は部分的に結合した成分の部位があるように、成分の異なる配置は、結びつけられ得る。いくつかの場合において、各成分の厚さは、その範囲全体で均一であるが、厚さは変化してもよく、例えば、成分の周辺の厚さは、成分がドーム型に見えるような中心よりも小さくてもよい。このようなドーム型の成分の結合は、起伏している薄膜により担体材料の填補をもたらし、連続的に担体材料の全てを覆ってもよく、又は不連続的であってもよく、又は担体材料の表面全体を変えてもよい。 The form of the thin film catalyst coating exists as a component that can be a variety of different shapes, but is all characterized by the component of the thin film having a lateral dimension that is greater than the thickness direction. The component boundaries may be circular, rectangular, hexagonal, or other known geometric shapes, and the boundary shapes may be irregular. The components may be discontinuous without contact between adjacent components, may be in contact with adjacent components, or may be clearly combined with adjacent components so that one component dissolves into the other. When complete bonding of the components occurs, the thin film of the present invention becomes continuous. In any catalyst material produced by the method of the present invention, there are sites on the substrate that are covered with a thin continuous membrane, sites of discontinuous components, and sites of bonded or partially bonded components. Different arrangements of components can be combined. In some cases, the thickness of each component is uniform throughout its range, but the thickness may vary, for example, the thickness around the component is centered so that the component appears dome-shaped. May be smaller. Such dome-shaped component coupling results in the filling of the carrier material by the undulating film, which may continuously cover all of the carrier material, or may be discontinuous, or the carrier material You may change the entire surface.
薄膜触媒被覆は、≦８ｎｍ、適切には≦６ｎｍ、好ましくは≦５ｎｍの平均厚さを適切に有する。薄膜触媒被覆は、≧０．６ｎｍ、好ましくは≧１ｎｍ、最も好ましくは≧２ｎｍの平均厚さを適切に有する。該被覆の平均厚さは、当業者に知られている技術、例えば、薄膜触媒被覆全体で多数の測定をして平均値を計算することにより測定される。 The thin film catalyst coating suitably has an average thickness of ≦ 8 nm, suitably ≦ 6 nm, preferably ≦ 5 nm. The thin film catalyst coating suitably has an average thickness of ≧ 0.6 nm, preferably ≧ 1 nm, most preferably ≧ 2 nm. The average thickness of the coating is measured by techniques known to those skilled in the art, for example, by making a number of measurements across the thin film catalyst coating and calculating the average value.
担体材料は、本発明における使用に適するいかなる材料であってもよい。適切には、担体材料は、触媒材料が燃料電池の操作条件下で使用される場合、腐食に対して抵抗性がある。 The carrier material can be any material suitable for use in the present invention. Suitably, the support material is resistant to corrosion when the catalyst material is used under fuel cell operating conditions.
一つの実施態様において、担体材料は、繊維である。繊維は、適切には炭素（例えば、ポリアクリロニトリル、ポリイミド、セルロース等の炭化可能なポリマー）、ポリマー（例えば、ポリベンズイミダゾール、ポリイミド、ポリテトラフルオロエチレン（ＰＴＦＥ））、金属酸化物（例えば、ドープチタン酸化物又はドープスズ酸化物等の導電性金属酸化物）、導電性混合金属酸化物（例えば、ＰＣＴ特許出願ＰＣＴ／ＧＢ２０１１／０５２４７２号で開示されるように）、金属窒化物（例えば、窒化チタンのような導電性窒化物）、金属炭化物（例えば、炭化タングステン、炭化チタン等の導電性金属炭化物）、又は金属である。これらの繊維は、エレクトロスピニング法、フォーススピニング法、ロータリージェットスピニング法、溶融紡糸法、及び繊維を製造するために当業者に知られている他の一般的な技術により製造され得る。繊維担持材料は、適切には０．５μｍ、より適切には１μｍ、好ましくは３μｍより大きな長さと高アスペクト比を有する。繊維の最大の長さは、繊維の性質及び製造される方法に依存するであろう。「高アスペクト比」は、長さが横断面寸法よりもかなり大きいこと（例えば、少なくとも６倍、適切には少なくとも１５倍、及び好ましくは少なくとも３０倍）を意味する。適切には、繊維担持材料の最も大きな横断面寸法は、３０から５００ｎｍ、適切には３０から２００ｎｍ、及び好ましくは３０から１００ｎｍの範囲である。 In one embodiment, the carrier material is a fiber. The fibers are suitably carbon (eg, carbonizable polymers such as polyacrylonitrile, polyimide, cellulose, etc.), polymers (eg, polybenzimidazole, polyimide, polytetrafluoroethylene (PTFE)), metal oxides (eg, doped Conductive metal oxides such as titanium oxide or doped tin oxide), mixed conductive metal oxides (eg as disclosed in PCT patent application PCT / GB2011 / 052472), metal nitrides (eg titanium nitride) A conductive nitride), a metal carbide (for example, a conductive metal carbide such as tungsten carbide or titanium carbide), or a metal. These fibers can be produced by electrospinning, force spinning, rotary jet spinning, melt spinning, and other common techniques known to those skilled in the art for producing fibers. The fiber support material suitably has a length and high aspect ratio greater than 0.5 μm, more suitably 1 μm, preferably greater than 3 μm. The maximum length of the fiber will depend on the nature of the fiber and the method being manufactured. “High aspect ratio” means that the length is significantly greater than the cross-sectional dimension (eg, at least 6 times, suitably at least 15 times, and preferably at least 30 times). Suitably, the largest cross-sectional dimension of the fiber support material is in the range of 30 to 500 nm, suitably 30 to 200 nm, and preferably 30 to 100 nm.
第二の実施態様において、担体材料は、微粒子である。微粒子は、炭素粒子、例えば、市販の高表面積カーボンブラック（Ｃａｂｏｔ Ｃｏｒｐ（Ｖｕｌａｎ ＸＣ７２Ｒ）及びＡｋｚｏ Ｎｏｂｅｌ（Ｋｅｔｊｅｎ ｂｌａｃｋ ｓｅｒｉｅｓ)から購入可能なような）又はこれらのカーボンブラックのグラファイト版又はアセチレンブラック（Ｄｅｎｋａから入手可能）など他の市販のカーボンブラックであり得る。炭素は、国際特許出願ＰＣＴ／ＧＢ２０１２／０５２３０６号に記載されるように、燃料電池に使用するために特に設計されるものであり得る。あるいは、微粒子は、金属酸化物（例えば、チタニア、ジルコニア、シリカ、又は混合酸化物、特に、ニオブドープチタニア、リンドープスズ酸化物、混合白金族金属酸化物のような導電性混合酸化物、又は国際特許出願ＰＣＴ／ＧＢ２０１１／０５２４７２号に記載されるような混合金属酸化物）、炭化物（例えば、炭化タングステン又は炭化チタン）、窒化物、特に導電性窒化物、（例えば、窒化チタン又は窒化チタンアルミニウム）であり得る。 In a second embodiment, the carrier material is a microparticle. The microparticles are carbon particles, such as commercially available high surface area carbon black (such as those available from Cabot Corp (Vulan XC72R) and Akzo Nobel (Ketjen black series)) or graphite versions of these carbon blacks or acetylene black (from Denka). Other commercially available carbon blacks. The carbon may be specially designed for use in fuel cells, as described in International Patent Application PCT / GB2012 / 052306. Alternatively, the microparticles may be metal oxides (eg, titania, zirconia, silica, or mixed oxides, particularly conductive mixed oxides such as niobium doped titania, phosphorus doped tin oxide, mixed platinum group metal oxides, or international patents. Mixed metal oxides as described in application PCT / GB2011 / 052472), carbides (eg tungsten carbide or titanium carbide), nitrides, in particular conductive nitrides (eg titanium nitride or titanium aluminum nitride) possible.
いくつかの実施態様において、担体材料及び／又は（もし存在すれば）粘着層は、薄膜触媒被覆に対する異なる触媒反応のための触媒活性を有し得て、この場合、薄膜触媒被覆が担体材料及び／又は粘着層を完全に覆わないが、担体材料及び／又は粘着層が目に見えるように、一部の場所で存在しない。例えば、担体材料及び／又は粘着層は、酸素発生反応のための触媒として作用する導電性混合金属酸化物（上述のように）であり得る。担体材料及び／又は粘着層が、適切には２０から８０％、好ましくは４０から６０％の触媒活性を有する担体材料及び／又は粘着層は、薄膜触媒被覆により覆われていない。 In some embodiments, the support material and / or the adhesive layer (if present) can have catalytic activity for different catalytic reactions on the thin film catalyst coating, wherein the thin film catalyst coating is the support material and Does not completely cover the adhesive layer, but is not present in some places so that the carrier material and / or adhesive layer is visible. For example, the support material and / or the adhesion layer can be a conductive mixed metal oxide (as described above) that acts as a catalyst for the oxygen evolution reaction. The support material and / or the adhesion layer, where the support material and / or the adhesion layer suitably have a catalytic activity of 20 to 80%, preferably 40 to 60%, are not covered by the thin film catalyst coating.
本発明の方法により調製される触媒材料は、触媒層中での使用を有し、例えば、燃料電池のような電気化学的電池の電極中での使用のためである。触媒材料は、当業者に知られている多くの方法、例えば、インクの調製及びインクを膜又はガス拡散層に塗布することにより層中に生成され、又は印刷法、噴霧法、ロール式ナイフ法、粉体塗装法、電気泳動法等の標準的な方法により基材に転写される。担体材料がエレクトロスピニングされた繊維である実施態様において、担体材料の予め生成される層は、創出され得て、薄膜触媒被覆は、その後、該担体材料の予め生成される層に塗布され、自立の触媒層を提供する。該自立の触媒層は、その後、単純な積層方法により基材（例えば、膜又はガス拡散層）に塗布される。 The catalyst material prepared by the method of the present invention has use in the catalyst layer, for example for use in electrodes of electrochemical cells such as fuel cells. The catalyst material can be produced in a number of ways known to those skilled in the art, such as ink preparation and application of ink to a membrane or gas diffusion layer, or printing, spraying, roll knife methods. Then, it is transferred to the substrate by a standard method such as a powder coating method or an electrophoresis method. In embodiments where the support material is an electrospun fiber, a pre-generated layer of support material can be created and a thin film catalyst coating is then applied to the pre-generated layer of the support material and is free standing. The catalyst layer is provided. The free-standing catalyst layer is then applied to a substrate (eg a membrane or gas diffusion layer) by a simple lamination method.
触媒層は、一よりも多い異なる種類の本発明の触媒材料を含み得て、該異なる種類の触媒材料は、同じ触媒機能を有するか又は異なる触媒機能を有する。例えば、触媒層は、異なる担体材料及び／又は異なる薄膜触媒被覆を有する本発明の触媒材料を含み得る。触媒材料のいくつかは、中間層を含んでもよく、含まなくてもよい。一よりも多い異なる種類の触媒材料が触媒層中で使用されるならば、異なる触媒は、混合されてもよく、あるいは別々の層中又は２つの層の組合せであってもよい。 The catalyst layer may include more than one different type of catalyst material of the present invention, the different types of catalyst material having the same catalytic function or different catalytic functions. For example, the catalyst layer may comprise a catalyst material of the present invention having a different support material and / or a different thin film catalyst coating. Some of the catalyst materials may or may not include an intermediate layer. If more than one different type of catalyst material is used in the catalyst layer, the different catalysts may be mixed or in separate layers or a combination of the two layers.
触媒層は、本発明の一又は複数の触媒層及びいくつか又は異なる触媒機能を有する一又は複数の一般的なナノパーティキュレート触媒を含み得る。例えば、本発明の触媒材料が酸素還元反応又は水素酸化反応のために使用される場合、一般的な触媒成分は、酸素発生反応に対して活性であり、又は逆も同様である。 The catalyst layer may include one or more catalyst layers of the present invention and one or more common nanoparticulate catalysts having several or different catalytic functions. For example, when the catalyst material of the present invention is used for an oxygen reduction or hydrogen oxidation reaction, the general catalyst components are active for the oxygen evolution reaction, or vice versa.
担体材料の形態が繊維状であるか又は高アスペクト比であるならば、その場合、触媒材料は、触媒層の面積の中で等方的に配置され（すなわち、全ての繊維が同一の方向に配向され）、該材料の充填密度を高くし、層の空隙率を減少し得る。触媒層の望ましい構造により、等方性が高度に配向からランダムに配向（異方性）へ変化し得ることは、明らかであろう。 If the form of the support material is fibrous or has a high aspect ratio, then the catalyst material is placed isotropically within the area of the catalyst layer (ie all fibers are in the same direction). Oriented) to increase the packing density of the material and reduce the porosity of the layer. It will be apparent that the desired structure of the catalyst layer can change the isotropic property from highly oriented to randomly oriented (anisotropic).
触媒層の厚さは、適切には≦１００μｍ、より適切には≦２０μｍ、好ましくは≦１０μｍ、及び最も好ましくは≦５μｍである。適切には、触媒層の厚さは、≧０．３μｍ、好ましくは≧０．５μｍである。 The thickness of the catalyst layer is suitably ≦ 100 μm, more suitably ≦ 20 μm, preferably ≦ 10 μm, and most preferably ≦ 5 μm. Suitably the thickness of the catalyst layer is ≧ 0.3 μm, preferably ≧ 0.5 μm.
触媒材料の空隙率は、適切には≧２０％、好ましくは≧４０％、及び最も好ましくは５０から７０％である。 The porosity of the catalyst material is suitably ≧ 20%, preferably ≧ 40%, and most preferably 50 to 70%.
触媒層は、追加の成分も含んでもよい。このような成分は、以下に限られないが、プロトン伝導体（例えば、パーフルオロスルホン酸（ＰＦＳＡ）ポリマー（例えば、Ｎａｆｉｏｎ（登録商標））のような高分子又は水性電解質、炭化水素プロトン伝導性ポリマー（例えば、スルホン化ポリアリーレン）、又はリン酸）、水の移送を制御するための疎水性添加物（ＰＴＦＥのようなポリマー又は表面処理された若しくはされない無機固体）又は親水性（ポリマー又は酸化物のような無機固体）添加物、例えば、過酸化水素の分解のための活性を有する追加の触媒材料（例えば、セリア又は二酸化マンガン）を含む。 The catalyst layer may also include additional components. Such components include, but are not limited to, polymer or aqueous electrolytes such as proton conductors (eg, perfluorosulfonic acid (PFSA) polymers (eg, Nafion®), hydrocarbon proton conductivity Polymers (eg, sulfonated polyarylene) or phosphoric acid), hydrophobic additives to control water transport (polymers such as PTFE or inorganic solids with or without surface treatment) or hydrophilic (polymer or oxidation) Inorganic solids) additives, for example, additional catalyst materials (eg, ceria or manganese dioxide) that have activity for the decomposition of hydrogen peroxide.
触媒層の触媒材料が、触媒層中に形成される前に、熱処理又は電気化学サイクルを予め受けていなければ、触媒層上でこの処理を実施することは有益であり得て、低配位金属原子の数を減らすか、さもなければ薄膜触媒被覆の形態が変化する。 If the catalyst material of the catalyst layer has not previously been subjected to a heat treatment or electrochemical cycle before it is formed in the catalyst layer, it may be beneficial to perform this treatment on the catalyst layer, and the low coordination metal Reduce the number of atoms or otherwise change the morphology of the thin film catalyst coating.
本発明の方法により調製される触媒材料は、ガス拡散層（ＧＤＬ）を含む電極及び触媒材料を含む触媒層にも使用され得る。典型的なガス拡散層は、適切には剛性シート炭素繊維紙（例えば、日本のＴｏｒａｙ Ｉｎｄｕｓｔｒｙ社から入手可能なＴＧＰ−Ｈシリーズの炭素繊維紙）のような一般的な不織炭素繊維ガス拡散基材、又はロールグッド（ｒｏｌｌ−ｇｏｏｄ）炭素繊維紙（例えば、ドイツのＦｒｅｕｄｅｎｂｅｒｇ ＦＣＣＴ ＫＧから入手可能なＨ２３１５ベースシリーズ；ドイツのＳＧＬ ＴｅｃｈｎｏｌｏｇｉｅｓＧｍｂＨから入手可能なＳｉｇｒａｃｅｔ（登録商標）シリーズ；米国のＢａｌｌａｒｄ Ｍａｔｅｒｉａｌ Ｐｒｏｄｕｃｔｓから入手可能なＡｖＣａｒｂ（登録商標）シリーズ；又は台湾のＣｅＴｅｃｈ株式会社から入手可能なＮ０Ｓシリーズ））、又は織物炭素繊維布基材（例えば、イタリアのＳＡＡＴＩ Ｇｒｏｕｐ，Ｓ．ｐ．Ａ．から入手可能な炭素布のＳＣＣＧシリーズ；又は台湾のＣｅＴｅｃｈ株式会社から入手可能なＷ０Ｓシリーズ）に基づく。多くのＰＥＭＦＣ及び直接メタノール燃料電池（ＤＭＦＣ）用途では、不織炭素繊維紙又は織物炭素繊維布基材は、典型的には疎水性ポリマー処理及び／又は基材内に埋め込まれるか又は平坦な面に被覆された微粒子材料を含む微孔性層への適用、又は両方の組み合わせで変性してガス拡散層が形成される。微粒子状材料は、典型的にはカーボンブラックとポリテトラフロオロエチレン（ＰＴＦＥ）のようなポリマーの混合物である。適切には、ガス拡散層は１００から４００μｍの厚さである。好ましくは、触媒層と接触するガス拡散層の面上にカーボンブラックとＰＴＦＥのようなパティキュレートマテリアルの層が存在する。 The catalyst material prepared by the method of the present invention can also be used for an electrode including a gas diffusion layer (GDL) and a catalyst layer including a catalyst material. A typical gas diffusion layer is suitably a common non-woven carbon fiber gas diffusion group such as a rigid sheet carbon fiber paper (eg, TGP-H series carbon fiber paper available from Toray Industry, Japan). Materials, or roll-good carbon fiber paper (e.g., the H2315 base series available from Freudenberg FCCT KG, Germany; the Sigracet (R) series available from SGL Technologies GmbH, Germany; AvCarb® series available; or NOS series available from CeTech Co., Ltd. in Taiwan), or woven carbon fiber fabric substrates (eg, SAATI Group, SpA, Italy). SCCG series Luo available carbon cloth; or from Taiwan of CeTech Co., Ltd. based on the W0S series) available. In many PEMFC and direct methanol fuel cell (DMFC) applications, the non-woven carbon fiber paper or woven carbon fiber fabric substrate is typically embedded in a flat surface with a hydrophobic polymer treatment and / or substrate. The gas diffusion layer is formed by modification to the microporous layer containing the particulate material coated on the surface, or a combination of both. The particulate material is typically a mixture of polymers such as carbon black and polytetrafluoroethylene (PTFE). Suitably, the gas diffusion layer is 100 to 400 μm thick. Preferably, there is a layer of particulate material such as carbon black and PTFE on the surface of the gas diffusion layer in contact with the catalyst layer.
ＰＥＭ燃料電池において、電解質はプロトン伝導性膜である。本発明の方法により調製される触媒材料を含む触媒層は、プロトン伝導性膜の片面又は両面に付着されて触媒化膜を形成し得る。 In PEM fuel cells, the electrolyte is a proton conducting membrane. The catalyst layer containing the catalyst material prepared by the method of the present invention can be deposited on one or both sides of the proton conducting membrane to form a catalyzed membrane.
膜は、ＰＥＭＦＣにおける使用に適切ないかなる膜であってもよく、例えば、膜は、Ｎａｆｉｏｎ（登録商標）（ＤｕＰｏｎｔ）、Ａｑｕｉｖｉｏｎ（登録商標）（Ｓｏｌｖａｙ−Ｐｌａｓｔｉｃｓ）、Ｆｌｅｍｉｏｎ（登録商標）（旭硝子）、及びＡｃｉｐｌｅｘ（登録商標）（旭化成）のようなパーフルオロ化スルホン酸料に基づくものであってもよい。あるいは、膜は、ｆｕｍａｐｅｍ（登録商標）Ｐ、Ｅ又はＫシリーズ製品としてＦｕＭＡ−Ｔｅｃｈ ＧｍｂＨ、ＪＳＲ社、東洋紡社等から入手可能なもののようなスルホン化炭化水素膜に基づくものであってもよい。膜は、プロトン伝導性材料、及び機械強度のような性質を与える他の材料を含む複合膜であってもよい。例えば、膜は、延伸ＰＴＦＥ基材を含み得る。あるいは、膜は、リン酸がドープされたポリベンズイミダゾールに基づいてもよく、ＢＡＳＦ Ｆｕｅｌ Ｃｅｌｌ ＧｍｂＨのような開発会社からの膜、例えば、１２０℃から１８０℃の範囲で作動するＣｅｌｔｅｃ（登録商標）−Ｐ膜を含んでもよい。他の成分は、例えば、耐久性を向上させるために、当業者に知られているようなものは、膜に添加されてもよい。 The membrane may be any membrane suitable for use in PEMFC, for example, the membrane may be Nafion® (DuPont), Aquivion® (Solvay-Plastics), Flemion® (Asahi Glass). And perfluorinated sulfonic acid materials such as Aciplex® (Asahi Kasei). Alternatively, the membrane may be based on a sulfonated hydrocarbon membrane such as those available from FuMA-Tech GmbH, JSR, Toyobo etc. as a fumapem® P, E or K series product. The membrane may be a composite membrane comprising a proton conducting material and other materials that impart properties such as mechanical strength. For example, the membrane can include an expanded PTFE substrate. Alternatively, the membrane may be based on phosphoric acid doped polybenzimidazole, a membrane from a development company such as BASF Fuel Cell GmbH, for example Celtec® operating in the range of 120 ° C. to 180 ° C. -P film may be included. Other ingredients may be added to the membrane, such as those known to those skilled in the art, for example to improve durability.
触媒層が塗布される基材は、転写基材であってもよい。転写基材は、当業者に知られるいかなる適切な転写基材であり得るが、好ましくはポリテトラフルオロエチレン（ＰＴＦＥ）、ポリイミド、ポリビニリデンジフルオリド（ＰＶＤＦ）、若しくはポリプロピレン（特に二軸延伸ポリプロピレン、ＢＯＰＰ）のようなポリマー材料、又はポリウレタンコート紙のようなポリマーコート紙である。転写基材は、シリコーン剥離紙又はアルミニウム箔のような金属箔であってもよい。本発明の触媒層は、その後、当業者に知られた技術によりＧＤＬ又は膜に転写され得る。 The substrate to which the catalyst layer is applied may be a transfer substrate. The transfer substrate can be any suitable transfer substrate known to those skilled in the art, but is preferably polytetrafluoroethylene (PTFE), polyimide, polyvinylidene difluoride (PVDF), or polypropylene (especially biaxially oriented polypropylene, Polymer material such as BOPP) or polymer coated paper such as polyurethane coated paper. The transfer substrate may be a silicone release paper or a metal foil such as an aluminum foil. The catalyst layer of the present invention can then be transferred to the GDL or membrane by techniques known to those skilled in the art.
本方法により調製される触媒材料は、上述のように触媒層、電極又は触媒化膜を含む膜電極接合体中に存在し得る。ＭＥＡは、下記のものを含むが、それに制限されない多くの方法で作製され得る：
（ｉ）プロトン伝導性膜は、少なくとも一つが本発明による電極である二つの電極（一つのアノードと一つのカソード）の間に挟まれ得る；
（ｉｉ）触媒層のみ片面に被覆される触媒化膜は、（ａ）触媒層で被覆される膜の側と接触するガス拡散層と電極との間に挟まれ得るか、又は（ｂ）二つの電極の間に挟まれ得る、ここで、触媒層と電極の少なくとも一つが本発明による触媒層を含む；
（ｉｉｉ）触媒層の両面に被覆される触媒化膜は、（ａ）二つのガス拡散層、（ｂ）ガス拡散層と電極、又は（ｃ）二つの電極の間に挟まれ得る、ここで、触媒層と電極の少なくとも一つが本発明による触媒層を含む。
The catalyst material prepared by this method may be present in a membrane electrode assembly comprising a catalyst layer, electrode or catalyzed membrane as described above. MEAs can be made in a number of ways, including but not limited to:
(I) The proton conducting membrane can be sandwiched between two electrodes (one anode and one cathode), at least one of which is an electrode according to the present invention;
(Ii) The catalytic membrane coated only on one side of the catalyst layer can be sandwiched between the gas diffusion layer and the electrode in contact with the side of the membrane coated with the catalyst layer (a) or (b) Can be sandwiched between two electrodes, wherein at least one of the catalyst layer and the electrode comprises a catalyst layer according to the present invention;
(Iii) The catalyzed membrane coated on both sides of the catalyst layer may be sandwiched between (a) two gas diffusion layers, (b) a gas diffusion layer and an electrode, or (c) two electrodes, At least one of the catalyst layer and the electrode includes the catalyst layer according to the present invention.
ＭＥＡは、例えば、国際公開第２００５／０２０３５６号に記載されているように、ＭＥＡの辺領域を密封及び／又は補強する成分を更に含み得る。ＭＥＡは当業者に知られる一般的な方法により組み合わされる。 The MEA may further include a component that seals and / or reinforces the edge region of the MEA, for example, as described in WO 2005/020356. MEAs are combined by common methods known to those skilled in the art.
本発明の方法により調製される触媒材料は、多くの応用、例えば、ＰＥＭＦＣ、又はリン酸電解質燃料電池（ＰＡＦＣ）のような液体酸性電解質を利用する燃料電池に使用され得て、及び特にカソード（好ましくは第１金属が白金である場合）で酸素還元反応のために使用され得る。ＰＥＭＦＣ又はＰＡＦＣは、アノードで水素又は水素リッチ燃料により作動するか、又はメタノールのような炭化水素燃料で供給され得る。本発明の方法により調製される触媒材料は、ＰＥＭＦＣ又はＰＡＦＣのアノードで使用され、これらの燃料でも作動し得る。 The catalyst material prepared by the method of the present invention can be used in many applications, for example, fuel cells that utilize liquid acidic electrolytes such as PEMFC, or phosphate electrolyte fuel cells (PAFC), and in particular cathodes ( Preferably when the first metal is platinum) it can be used for the oxygen reduction reaction. The PEMFC or PAFC can operate with hydrogen or hydrogen rich fuel at the anode, or be supplied with a hydrocarbon fuel such as methanol. The catalyst material prepared by the process of the present invention is used in PEMFC or PAFC anodes and can also operate with these fuels.
本発明の方法により調製される触媒材料は、プロトン以外の電荷キャリアを使用する固体高分子膜、例えばＴｏｋｕｍａ Ｓｏｄａ社、ＦｕＭＡ−Ｔｅｃｈ ＧｍｂＨから入手可能なもののようなＯＨ−伝導性膜、の中の燃料電池のカソード又はアノードでも使用され得る。 The catalyst material prepared by the method of the present invention includes solid polymer membranes that use charge carriers other than protons, such as OH - conductive membranes such as those available from Tokuma Soda, FuMA-Tech GmbH. It can also be used in the cathode or anode of a fuel cell.
本発明の方法により調製される触媒材料は、水性酸及びアルカリ性溶液又は濃リン酸のような液体イオン伝導性電解質を用いる他の低温燃料電池でも使用され得る。 The catalyst material prepared by the method of the present invention can also be used in other low temperature fuel cells using liquid ion conducting electrolytes such as aqueous and alkaline solutions or concentrated phosphoric acid.
更に、本発明の方法により調製される触媒材料は、ＰＥＭ電気分解装置又はアルカリ性電解質に基づく電気分解装置中の水素発生電極又は酸素発生電極としても使用され得る。 Furthermore, the catalyst material prepared by the method of the present invention can also be used as a hydrogen generating electrode or an oxygen generating electrode in a PEM electrolyzer or an electrolyzer based on an alkaline electrolyte.
Claims (10)
前記方法は、
（ｉ）原子層堆積法又は化学蒸着法を用いて該担体材料上に第二金属の多層薄膜被覆を設ける工程、及び
（ｉｉ）前記一種又は複数種の第一金属による第二金属の少なくとも一部の自発的なガルバニック置換工程
を含み、
該第二金属は、一種又は複数種の該第一金属よりも貴でない、方法。 A method for preparing a catalyst material comprising a support material that is a fiber or a particulate material having a cross-sectional dimension in the range of 30 to 500 nm and (ii) a thin film catalyst coating, said coating Comprises one or more first metals and optionally a second metal;
The method
(I) providing a multilayer thin film coating of a second metal on the support material using atomic layer deposition or chemical vapor deposition ; and (ii) at least one of the second metals from the one or more first metals. Part of the galvanic replacement process,
The method wherein the second metal is less noble than the one or more first metals.
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| GB1214326.9 | 2012-08-10 | ||
| GBGB1214326.9A GB201214326D0 (en) | 2012-08-10 | 2012-08-10 | Process |
| PCT/GB2013/052085 WO2014023944A1 (en) | 2012-08-10 | 2013-08-05 | Process for preparing a catalytic material |
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| JP6395212B2 (en) * | 2014-08-29 | 2018-09-26 | 株式会社キャタラー | Method for producing exhaust gas purification catalyst |
| US9633957B2 (en) * | 2014-11-28 | 2017-04-25 | Infineon Technologies Ag | Semiconductor device, a power semiconductor device, and a method for processing a semiconductor device |
| KR101815999B1 (en) | 2016-01-25 | 2018-01-09 | 서울대학교산학협력단 | Fabrication method of whisker catalyst using galvanic displacement reaction and whisker catalyst |
| EP3509743A4 (en) * | 2016-09-08 | 2020-05-13 | The Board of Trustees of the Leland Stanford Junior University | Atomic layer deposition of electrochemical catalysts |
| EP3509744A4 (en) | 2016-09-08 | 2020-05-20 | The Board of Trustees of the Leland Stanford Junior University | Atomic layer deposition with passivation treatment |
| EP3638404A4 (en) | 2017-06-13 | 2021-03-10 | The Board of Trustees of the Leland Stanford Junior University | Electrochemical catalysts with enhanced catalytic activity |
| EP3453785A1 (en) * | 2017-09-07 | 2019-03-13 | Kabushiki Kaisha Toshiba | Membrane electrode assembly, electrochemical cell, and electrochemical device |
| US20190109330A1 (en) * | 2017-10-09 | 2019-04-11 | Uchicago Argonne, Llc | Thin-film catalyst with enhanced catalyst-support interactions |
| CN110085875B (en) * | 2019-04-19 | 2022-06-17 | 同济大学 | Multi-layer catalyst layer for relieving attenuation of alloy-containing catalyst layer and preparation method thereof |
| WO2023058624A1 (en) * | 2021-10-08 | 2023-04-13 | コニカミノルタ株式会社 | Dyeing method, evaluation method and sample |
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| US5879827A (en) | 1997-10-10 | 1999-03-09 | Minnesota Mining And Manufacturing Company | Catalyst for membrane electrode assembly and method of making |
| JP2004025151A (en) * | 2002-06-28 | 2004-01-29 | Aisin Seiki Co Ltd | Method of supporting catalyst |
| GB0319780D0 (en) | 2003-08-22 | 2003-09-24 | Johnson Matthey Plc | Membrane electrode assembly |
| US7723894B2 (en) | 2004-12-20 | 2010-05-25 | General Electric Company | Electrical machine with improved loss characteristics and method of making same |
| WO2009135189A1 (en) | 2008-05-01 | 2009-11-05 | Monsanto Technology Llc | Metal utilization in supported, metal-containing fuel cell catalysts |
| US20100099012A1 (en) | 2008-10-17 | 2010-04-22 | Brookhaven Science Associates, Llc | Electrocatalyst Synthesized by Depositing a Contiguous Metal Adlayer on Transition Metal Nanostructures |
| US8404613B2 (en) * | 2008-10-21 | 2013-03-26 | Brookhaven Science Associates, Llc | Platinum-based electrocatalysts synthesized by depositing contiguous adlayers on carbon nanostructures |
| WO2010107822A2 (en) | 2009-03-16 | 2010-09-23 | University Of Massachusetts | Methods for the fabrication of nanostructures |
| JP5303483B2 (en) * | 2010-01-27 | 2013-10-02 | 株式会社豊田中央研究所 | Ozone decomposition removal catalyst, method for producing the same, and ozone decomposition removal method using the same |
| JP5573438B2 (en) * | 2010-07-09 | 2014-08-20 | トヨタ自動車株式会社 | Method for producing core-shell type catalyst fine particles |
| GB201021352D0 (en) | 2010-12-16 | 2011-01-26 | Johnson Matthey Plc | Catalyst layer |
| JP5674553B2 (en) * | 2011-05-11 | 2015-02-25 | 株式会社豊田中央研究所 | Ozone decomposition removal catalyst, method for producing the same, and ozone decomposition removal method using the same |
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| WO2013144631A1 (en) | 2012-03-30 | 2013-10-03 | Johnson Matthey Fuel Cells Limited | Thin film catalytic material for use in fuel |
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| GB201214326D0 (en) | 2012-09-26 |
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